Disazo dyes for cellulose esters and ethers



Patented June 3, 1941 UNITED STATES PATENT OFFIQE Donovan E. Kvalnes, Perms Grove, N. 3., assignor to E. I. du Pont de Nemours & Company, Wilmington, 'Del., a. corporation of Delaware No Drawing. Application November 2-2, 1939, Serial No. 305,656

9 Claims.

This invention relates to disazo dyes which are especially useful for dyeing cellulose esters and ethers, such as cellulose acetate silk and to processes for manufacturing the same, and especially to dyes having a general formula provide dyes which have good afiinity for cellulose acetate and will yield deep shades of blue, bluish green and black. Another object is to provide processes for preparing such dyes. Still other objects of the invention will be apparent from the following description.

The objects of the invention are attained in general by providing compounds represented by the general formula and applying them to the fibers or materials to be. dyed. The objects are attained in part by providing compounds which are obtainable by diazotizing a, para nitro aniline or naphthylamine or a mono N-substituted paraarylene diamine of the benzene or naphthalene series, coupling with a suitable benzene or naphthalene tertiary amine, transforming the nitro or N-substituent of the arylene diamine nucleus to amino to give an arylazo compound represented by the formula diazotizing this monazo compound, and then coupling with a mono N -substituted 1:5-amino naphthol.

The invention will be more fully set forth in the following more detailed description which includes examples that are given as illustrative embodiments of the invention and as limitations thereof.

Example 1 180 parts of oxalyl para-phenylene diamine were dissolved in 2500 parts of water and 110 parts of 28.5% ammonia solution. The solution was cooled to 0-5 C. by the addition of ice and 69 parts of sodium nitrite were added. This solution was slowly added to 1000 parts of water and 360 parts of a 31.5% hydrochloric acid solution whilst cooling with ice to 0-5 C. When diazotization was complete a solution of 195 parts of di(hydroxethyl) m-toluidine in 1000 parts of water and 1000parts of 31.5% hydrochloric acid solution was added to the diazo. Dilute sodium hydroxide solution was then added slowly until the mixture was only slightly acid to litmus paper. After stirring for two to three hours at 10 C. coupling was complete. Enough solid sodium hydroxide was added to give a 5% solution and the temperature was slowly raised to C. and held there two hours or until hydrolysis was complete. The reaction mixture was cooled to 20 C. and filtered and the residue was washed with sufficient cold water to free it from alkali and dried.

314 parts of the dry material were dissolved in 1000 parts of water containing 300 parts of 31.5% hydrochloric acid and cooled with ice to 0 C. The compound was diazotized by the addition of 69 parts of sodium nitrite dissolved in 200 parts of water. The diazo solution was then added to a solution of 203 parts of N(hydroxyethyl) 1,5- amino naphthol in 8000 parts of water and parts of 31.5% hydrochloric acid. Coupling was completed by the slow addition of sodium acetate solution until the reaction mixture was neutral to Congo red paper. The dye was isolated from a neutral solution, washed with water and dried. The compound is represented by the formula (H o CzHOzNQN=NON=N OH: HO

When dispersed in an aqueous medium with a suitable dispersing agent, such as soap the product dyed cellulose acetate in heavy blue shades of good fastness to light, which discharged to a white upon applying a, suitable discharge agent.

Example 2 271 parts of methyl, sorbityl aniline, obtained by the treatment of sorbityl aniline with dimethyl sulfate, were substituted for the di(hydroxyethyl) m-toluidine used in Example 1. A dye was obtained which readily dispersed and which dyed cellulose acetate heavy navy blue shades. from the diazo component which is a mono The dye is represented by the formula N-substituted para-phenylene diamine, such as HOCHKCHOHMCHZ NGN= ON=N 8NHC.H.OH CHa Emample 3 formyl-, acetyl-, oxaly1-, benzoyl-, arylsulfoiiylamino para-phenylene diamine or a para-nitro An e uivalent arrount of sorbit l, h droxy q 1 y y aniline. In making the compounds the diazo ethyl aniline, obtained by heating sorbityl aniline with an excess of 40% ethylene chlorhydrin in component was diazotized and coupled with the the presence of chalk, was used instead of thefirst component recited in thelfolmula and then di(hydroxy ethyl) m-toluidine in Example 1. A the terminal acylarmino Intro group of the dye which is represented by formula, was obmonazo compound. was hydrolized OI reduced, as tained. the case may be, to amino, thus giving a terminal HO CH2(CHOH)iCHz-lTT N=N- N=N NHCZH-l u HO C2H4 This product is readily dispersed and it dyed diazotizable amino group. Terminal hydrolizable cellulose acetate a heavy reddish blue shade which groups On the mOHaZO Compounds, c as y discharged to a white. amino were transformed to amino groupsby a Example 4 method similar to that described in Example 1.

When the diazo component was a para-nitro An equivalent amount of N-sorbityl, 1,5-amino aniline or naphthylamine, the terminal nitro naphthol; prepared by refluxing l,5'-amino naphgroup of the monazo compound Was transformed thol and glucose in alcohol'and reducing with a to amino by reduction, such as by heating the nickel catalyst, was substituted for the N-hymonazo compound with one and one-half moles clroxy ethyl 1,5-amin0naphtho1 in Example 1. of sodium sulfide in alkaline medium until the A dye was obtained which is represented by the nitro group was reduced. The arrows point tofollowing formula ward the compounds which were usedas the cou- CH3 HO This product built up on the fiber to give very pling components. The indicated colors are those heavy blue to nearly black shades. obtained by dyeing acetate silk in aqueous dis In the following examples the arrows point persons or solutions of the compounds,

Color on cellu- Color on ccllu- Example Compound. lose acetate Example Compound lose acetat Si silk 5 Dimethyl aniline p-niti'o aniline, Bluish grey. 17 Di(hydrcxy ethyl) 2,5-dimethoxy an- Navy blue. reduced N-(hydroxyethyD-Lfiiline 5-nitro2-aminoanisol, reamino naphtliol. duoed' N-(hydroxy ethyl)-1,5-

(3 Di (hydroxy ethyl) aniline oxalyl Reddish blue. amino naphthol.

R-plienylene diaininc, hydrolyzed-a 18; Di(l1ydi'oxy ethyl) 2,5-dimethoiiy ani- G1'( ,@ni hb] 1( i -(hydroxy ethyl)-l,57ainino naphline 2,5411 ethoxy para-phenylenc tho]. diiimine N-(hydroxy ethyl)-1,5-

7; Ethyl, hydroxy ethyl aniline iormyl Navy blue. amino naphthol.

p-phenylene diaminahydrolyzed- 19 Di(hydi'oxy;cthyl) o-anisidine 5, R d i m N-(hydroxy ethyl)-l,5aiiiino naphnitro-2-atnino anisol, reduced N- thol. 4 hydroxy ethyl)-l,5-amiiio naphtha].

g Di (hydroxy ethyl) aniline 5-iiitro- Do. 20 Sorbityl, hydroxy ethyl H1-t0il11dl!lG Navy blue. Z-amino anisol, reduced N-(hybenzoylp-phenyleiiediainine,hydrodroxy ethyl)-l,5-amino naphthol. I lyzed N-(hydroxy cthyl)-l,5-

9 Bis (dihydroxy pi-opyl) 811111116 Reddlsh blue. aminonaphthol.

aeetyl p-phenylene diainine, hydro- 21 Di(liy droxy ethyl) aniline p-nitro Rmdjgh b11115, lyzed N-(hydlOXY ethy1)-l,5- aniline, ldl1G0(ll.-)- N-sorbityl 1,5- amino naphthol. amino naphthol.

10 Di (hydroxy ethyl) in-toluidine 5- Navy blue. 22 Di(hydroxy ethyl) rn-toluidine 2- 13m nitro-2-amino-anisol, reduced 'N- chlo i-nitro aniline, reduced.. .N-

11 Di(hydroxy ethyl) mtoiuidineeait- Greenish blue. 23 diydroxyethy on s d ne 5* Reddish blue.

dimethoxy para-phenylenc diamine nitro-2-am1no-enisol, reduced N- N-(hydroxy ethyl)-l,5-amino s0r bityl1,5-amino naphthol. naphthol. 24 Soi'bityl, hydroxy ethyl aniline ox- D 12 Di (hydroxy ethyl) m-toluidine Do, elyl p-phenylene diaminc, hydronitro eresidine, reduced N-(liylyzed-a N-sorbityl 1,5-amino naphdroxy ethyl)-l,5-amino naphthol. thol.

13 Di (hydroxy etliyl),m-toluidine 2- (lear blue. 25 Sorbityl aniline condensed with 7 '[)i) chlor-4nitro aniline, reduced N- moles ethylenooxidee p-nitro ani- (hydroxy ethyl)-l.5-amino naphthol. line, reduced N-(hydroxy ethyl)- 14 Di (hydroxy ethyl) m-toluidine 4- Blue. 1,5-amin0 naphthol.

nitro-l-naphthylaminc, reduced 26 .l 'letialiydroxy ethyl rp-phenylene 1m N-(hydroxy ethyl)-l,5-amino naphdlfimme' p-nitro aniline,- reduced m i, N-(hydroxy ctliyl)-l,5-amino 15 Di (hydroxy ethyl) 2,5-dimethoxy Clear blue. naphthol.

aniline(-benzenesulfonylp-phenyl- 27 Aniline condensed with;6 moles. of .Rcddish blue. one diamine, hydrolyzed N-(hyethylene oxide p-nitro aniline, droxyethylhLfi-amino naphthol. reduced N-(hydroxy etliyl)-1,5

l6 Di (hydroxy ethyl) 2,5-diinethoxy Grcenish blue, amino naphthol. aniline (-nitro Cl'6S1diIl6,I dllC8d-) 28 Ethyl, hydroxy ethyl-l-nephthyl- Blue. N-(hydroxy ethyl)-l,5-ainino naphamine DDlfilO aniline, reduced th L N-(liydi'oxy cthyl)-l,5-iimino naphthol.

The compounds of the invention. are r'epresented generally by the formula NHRa The tertiary aryl aminesiwhich may be used as the first component comprise benzene and naphthalene compounds of the type in which R1 and R2 are alike or unlike and may be lower alkyl, monoand poly-hydroxyalkyl, or poly-ethenoxy. Examples of such groups are methyl, ethyl, propyl, butyl, hydroxyethyl, hydroxypropyl, dihydroxypropyl, monoand dihydroxybutyl, sorbityl, pentaerythrityl and other hydroxyalkyls having four to six carbons and one less hydroxy than carbons which are either straight or branched chain aliphatics, and various polyethenoxy groups or mixtures thereof which can be made by reacting an aniline or naphthylamine with 3 to 6 moles of ethylene oxide and thereby producing compounds having two terminal hydroxyethyl groups and one to four ether linkages of the type (CHzOH2O)n-1-CHzCH2OH Aryl-N (CHzCH)n1-CH2CH2OH in which n is an integer 1 to 5, such as C6H5N[ (CHzCI-IzO) 2CH2CH2OH] 2 CeHr-N (CHzCH2O)a-CH2CH2OH The substituents X in the general formula are one or more than one of the group consisting of hydrogen, alkyl, alkoxy, halogen, acylamino, dialkylamino, such as methyl, ethyl, propyl, butyl, the corresponding alkoxy groups, chloro, bromo, acetylamino, benzoylamino, dimethylamino and diethylamino. When aryli contains more than one substituent the substituent groups may be alike or unlike.

Arylz in the general formula is a benzene or naphthalene nucleus which may be substituted or not by the groups indicated as the substituents of aryli.

As illustrations of the group R3 the following are mentioned as representative, hydroxyethyl, monoand di-hydroxypropyl, monoand di-hydroxybutyl, sorbityl, pentaerythrityl and in general other hydroxyalkyl groups having four to six carbons and one less hydroxy than carbons and which are either straight or branched chain aliphatics, and the various polyethenoxy groups represented by R1. Erythrityl, arabinyl and mannityl are mentioned as other examples of hydroxyalkyl groups having 4 to 6 carbons and one less hydroxy groups than carbons.

It has been found that the compounds in which aryh and arylz are benzene nuclei and R1, R2 and R3 are from the group consisting of hydroxyalkyl and polyhydroxy alkyl, having 2 to 6 carbons, have particularly good affinity for acetate silk and are the preferred class.

' sample 1 was dispersed in 2000 parts of water containing 0.50 part of soap. The bath was heated to C. and a skein of cellulose acetate silk was entered. The skein was dyed for 45 minutes at 85 0., rinsed, washed and dried. The skein was evenly dyed a heavy blue shade having good fastn-ess to light. Upon applying a discharge agent, the dye discharged to white.

The mono-N-substituted 1:5-a-mino n-aphthols can be conveniently prepared by various methods. For example 1:5-amino-naphthol is reacted with the halide of the alkyl radical to be substituted in the amino group, such as pentaerythrityl bromide, BrCHa-C(CH2OH)3 giving N-pentaerythrityl 1:5-amino-naphthol. These compounds can also be made for example, by condensation and catalytic reduction of 1:5-amino naphthol with an aldose, such as mannose or glucose. The naphthols can also be made by reacting 1- 5-dihydroxy-naphthalene with the corresponding hydroxyalkyl amines and sodium bisulfite.

Since from the foregoing description of the invention it will be apparent to those skilled in the art that various other embodiments of the invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to the limitations which are specifically recited.

I claim: 1. Compounds represented by the formula Nar3| l1N=Nar ilzN=N NHR; R2 X dialkylamino; R1 and R2 are at least one of a group consisting of alkyl, m'onoand poly-hydroxyalkyl radicals having two to six carbons and polyethenoxy radicals represented by the formula (CHzCHzO) n-1CH2CH2OH in which n-l has a value of 1 to 4 and which are obtainable by condensing anilines and naphthylamines with two to six moles of ethylene oxide;

and R3 is one of a group consisting of monoand poly-hydroxyalkyl having two to six carbons.

2. Compounds represented by the formula NHR:

- (CHzGHzO) 11-1-CH2CH2OH in which n-l has a. value of 1 to 4 and which are obtainable by condensing anilines and naphthylamines with two. tosix moles of ethylene oxide; inuwhichrx is at least one of the group consisting and Riis oneofa; group consisting of monoand and dialkylamino.

poly-hydroxyalkyl having two to six carbon-s 8. The compound represented by the formula HOH4C2\ l /N I N=NC N'=N NHCHKCHOHMCHzOH Home? X HO l 3. Compounds representedby the-formula 10 of hydrogen, alkyl, alkoxy; halogen, acylamino Home, in which X is at least one of the group consisting of hydrogen, alkyl, alkoxy, halogen, acylamino and dialkylamino. R2 HO 9. The process which comprises diazotizing a inwhich each X is. at least one of a group concompaund represented by the formula sisting of hydrogen,alkyl, alkoxy, halogen, acyl- A Aryh NH2 amino and. dialkylamino; R2 is one' of a group consisting offalkyl, monoand poly hydroxyalkyl having two to sixlcar-bons and lpolyethenoxy'radin which amino andA are in para positions to icals' represented bythe formula each other, arylz is one of a group consisting of *(CI'hCH2O)1-CmCH2OH the nuclei of anilines and naphthylamines, A is which the value f is 1 and R3 one ofta group consisting of acylamino, sulfonylis one q group consisting mono and polyamino and nitro and X is at least one of a group hydroxyalkyl having two to six carbons; consisting of hydrogen, a y al hal en, 4 compounds represented by the for ula acylamino and dialkylamino; coupling with a tertiary aryl amine of the group consisting of benzene and naphthalene tertiary amines which are represented by the formula in which each X isat least one of a groupaconsisting of hydrogen, alkyl, alkoxy, halogen, acyl- 2 X amino and dialkylamino; and R1, R2 and R3 are each one of" a group consisting of hyd'roxyalkyl in which R1 and R2 are each one of a-group conand polyhydroX-yalkyl having two to six carbons. sisting of alkyl, m0n0- and p yy y y 5.-Compounds represented by the formula radicals having two to six carbons and poly- HOHC, ethenoxy radicals represented by the formula NN=N T -N=N NHC2H4OH 40 WW 110E402! HQ -(CH2CH2O)n-1CH2CH20H in which. each X is. at least one of a group. coninwhich hasa, Value of 1 to 4; transforming slsiimg'of hyqrogen, ailkyli alkoxy, halogen, 510371 the group A to amino; diazotizing the resulting ammo and dlalkylammomonazo" compound; and coupling with a com- 6, The compound represented by the formula pound represented by the formula HOH4C2\ N N=N-C N=N NHCzHiOH NHRL Home; no

HO in which X is at least one of 'thegroup consisting of hydrogen, alkyl, alkoxy, halogen, acylamino' and dialkylamino; in which R3 is one of a group consisting of mono- 7. Thecompound represented by the formula and poly-hydroxyalkyl having two to six carbons.

HOH4C2\ I ON=N -NHC2H4OH aoonncnonncm X. HO

DONOVAN E. KVALNES.

CERTIFICATE OF CORRECTI ON.

June 5, 1914.1.

Patent No. 2,2M ,559.

DONOVAN E. KVALNES.'

It is. hereby certified that error appears in the printed specification 7 of the above numbered patent requiring correction as follows: Page 1;, sec-' ond column, line 10, claim 8, strike out the words "of hydrogen, alkyl',

alkoxy, halogen, acylamino" and insert the same after "consisting" in same column, line 1, claim 7; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

- Signed and sealed this 29th day of July, A. D, l9l l.

Henry Van Arsdale,

Acting Commissioner of Patents.

(Seal) 

